Electrochemical Behavior of o‐Nitrophenol at Hexagonal Mesoporous Silica Modified Carbon Paste Electrodes

A hexagonal mesoporous silica (HMS) modified carbon paste electrode (CPE) was fabricated and characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) methods (ferrocene as a probe). The electrochemical behavior of nitrophenol (o‐NP) at the HMS modified electrode (HMSCPE) was investigated. Compared with CPE, a well‐defined reduction peak and a remarkably peak current response was observed. It is indicated that mesoporous HMS exhibited remarkable enhancement effects on the electrochemical reduction of o‐NP. The electrochemical reduction mechanism was also discussed. Consequently, a simple and sensitive electrochemical method was proposed for the determination of o‐NP, which was used to determine o‐NP in waste water samples.     

Electrochemical Investigation of Na‐Salt of 2‐Methyl‐3‐(4‐nitrophenyl)acrylate on Glassy Carbon Electrode

The electrochemical behavior of Na‐salt of 2‐methyl‐3‐(4‐nitrophenyl)acrylate (NPA) and its reduction product was studied by cyclic (CV), differential pulse(DPV) and square wave voltammetry (SWV) using a glassy carbon electrode (GCE). The results revealed that NPA is irreversibly reduced leading to the formation of a reduction product (P_NPA). For pH<9.0 the peak potential was linearly dependent on pH. For pH>9.0 the peak potential was pH‐independent and the value of pK_b≈9.0 was determined. The adsorbed P_NPA exhibited reversible redox reaction. The reduction of P_NPA was pH dependent. To ensure that the electrochemical behavior of NPA is due to the reducible moiety, NO₂, closely related compounds to NPA were also studied, and a redox mechanism was proposed for NPA.     

The Electrochemical Behavior of p‐tert‐Butyl‐sulfonylcalix[4]arene and Its Selective Complexation with Metal Ions at Water‐Air Interface

The electrochemical behavior of p‐tert‐butyl‐sulfonylcalix[4]arene (SCA) has been investigated by cyclic voltammetry. The results show that there is an irreversible electrochemical oxidative wave when the potential ranges from 0.9 to 1.9 V versus saturated calomel electrode (SCE) in CH₂Cl₂ at a glassy carbon electrode. The kinetic parameters of the andic wave, such as α,n, k_s, D and the diffusion activation energy (E_d), were discussed. In addition, the interaction of SCA with metal ions at the water‐air interface was also discussed by Langmuir‐Blodgett (LB) techniques. The results confirm that the selectivity of SCA as ligand for Pb²⁺ in monomolecular film is very high by complexation action, which provide the foundation that LB film of SCA modified glassy carbon electrode (GCE) as voltammetric sensor to detect trace amounts of Pb²⁺.     

Electrochemical Behavior of Apigenin at a Glassy Carbon Electrode and its Analytical Application

The electrochemical behavior of the antitumor herbal drug apigenin was studied in 0.1 mol L^?1 B‐R buffer solutions (50% ethanol, pH 3.0) by cyclic voltammetry (CV) at a glassy carbon electrode. In CV, two oxidation peaks (P₁ and P₂) with E_p1 = 1.03V and E_p2 = 1.23 V appeared at a scan rate of 0.05 V s^?1, and a new electroanalytical method for this herbal drug was established according to the oxidation peak P2. The peak currents have a linear relationship with apigenin concentration in a range from 9.0 × 10^?7 to 2.0 × 10^?5 mol L^?1. Using the established method, apigenin in a herbal drug was determined without pre‐separation with satisfactory results. Moreover, the electrode dynamics parameters were also investigated by electrochemical techniques and the possible electrode reaction mechanism was deduced.     

Graphene Functionalized Graphite Electrode with Diphenylacetylene for Sensitive Electrochemical Determination of Adenosine‐5′‐triphosphate

In this paper a molecular wire modified carbon paste electrode (MW‐CPE) was firstly prepared by mixing graphite powder with diphenylacetylene (DPA). Then a graphene (GR) and chitosan (CTS) composite film was further modified on the surface of MW‐CPE to receive the graphene functionalized electrode (CTS‐GR/MW‐CPE), which was used for the sensitive electrochemical detection of adenosine‐5′‐triphosphate (ATP). The CTS‐GR/MW‐CPE exhibited excellent electrochemical performance and the electrochemical behavior of ATP on the CTS‐GR/MW‐CPE was carefully studied by cyclic voltammetry with an irreversible oxidation peak appearing at 1.369 V (vs. SCE). The electrochemical parameters such as charge transfer coefficient (α) and electrode reaction standard rate constant (k_s) were calculated with the results of 0.53 and 5.28×10^?6 s^?1, respectively. By using differential pulse voltammetry (DPV) as detection technique, the oxidation peak current showed good linear relationship with ATP concentration in the range from 1.0 nM to 700.0 µM with a detection limit of 0.342 nM (3σ). The common coexisting substances, such as uric acid, ascorbic acid and guanosine‐5′‐triphosphate (GTP), showed no interferences and the modified electrode was successfully applied to injection sample detection.     

Direct Electrochemistry of Myoglobin in a Nafion‐Ionic Liquid Composite Film Modified Carbon Ionic Liquid Electrode

In this paper two kinds of ionic liquids (ILs) were used for the construction of a myoglobin (Mb) electrochemical biosensor. Firstly a hydrophilic ionic liquid of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIMBF₄) was used as binder to prepare a carbon ionic liquid electrode (CILE), then a Nafion and hydrophobic ionic liquid of 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆) composite film was applied on the surface of the CILE. The direct electrochemistry of Mb in the Nafion‐BMIMPF₆/CILE was achieved with the cathodic and anodic peak potentials located at ?0.345 V and ?0.213 V (vs. SCE). The formal potential (E°′) was located at ?0.279 V, which was the characteristic of Mb Fe^III/Fe^II redox couples. The electrochemical behaviors of Mb in the Nafion‐ionic liquid composite film modified CILE were carefully investigated. The Mb modified electrode showed good electrocatalytic behaviors to the reduction of trichloroacetic acid (TCA) and NaNO₂. Based on the Nafion‐BMIMPF₆/Mb/CILE, a new third generation reagentless biosensor was constructed.     

Electrocatalytic Oxidation and Voltammetric Determination of L‐Cysteic Acid at the Surface of p‐Bromanil Modified Carbon Paste Electrode

The electrochemical properties of L ‐cysteic acid studied at the surface of p‐bromanil (tetrabromo‐p‐benzoquinone) modified carbon paste electrode (BMCPE) in aqueous media by cyclic voltammetry (CV) and double step potential chronoamperometry. It has been found that under optimum condition (pH 7.00) in cyclic voltammetry, the oxidation of L ‐cysteic acid at the surface of BMCPE occurs at a half‐wave potential of p‐bromanil redox system (e.g., 100 mV vs. Ag|AgCl|KCl_sat), whereas, L ‐cysteic acid was electroinactive in the testing potential ranges at the surface of bare carbon paste electrode. The apparent diffusion coefficient of spiked p‐bromanil in paraffin oil was also determined by using the Cottrell equation. The electrocatalytic oxidation peak current of L ‐cysteic acid exhibits a linear dependency to its concentration in the ranges of 8.00×10^?6 M–6.00×10^?3 M and 5.2×10^?7 M–1.0×10^?5 M using CV and differential pulse voltammetry (DPV) methods, respectively. The detection limits (2σ) were determined as 5.00×10^?6 M and 4.00×10^?7 M by CV and DPV methods. This method was used as a new, selective, rapid, simple, precise and suitable voltammetric method for determination of L ‐cysteic acid in serum of patient's blood with migraine disease.     

Direct Electrochemistry of Hemoglobin in Layer‐by‐Layer Films Assembled with DNA and Room Temperature Ionic Liquid

Based on electrostatic interaction and electrodeposition, poly‐anionic deoxyribonucleic acid (DNA), room temperature ionic liquid 1‐butyl‐3‐methyl‐imidazolium tetrafluoroborate (BMIMBF₄), hemoglobin (Hb) and Poly(diallyldimethylammonium chloride) (PDDA) were successfully assembled into Hb/IL/DNA/PDDA layer‐by‐layer complex films on the surface of ITO electrode. FTIR spectroscopy, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to characterize the composite film. The obtained results demonstrated that the Hb molecule in the film kept its native structure and showed its good electrochemical behavior. A pair of well‐defined redox peaks of Hb with the formal potentials (E°′) of ?0.180 V (vs. SCE) was appeared in phosphate buffer solution (PBS, pH 7.0). The Hb/IL/DNA/PDDA/ITO modified electrode also showed an excellent electrocatalytic behavior to the reduction of hydrogen peroxide (H₂O₂). Therefore, the IL/DNA/PDDA complex film as a novel matrix open up a possibility for further study on the direct electrochemistry of other proteins and the fabrication of the third‐generation electrochemical biosensors.     

Fabrication of Electrochemical Reduced Graphene Oxide Films on Glassy Carbon Electrode by Pulsed Potentiostatic Methods and Its Electrochemical Application

A graphene‐based electrochemical sensing platform for sensitive determination of baicalein was constructed by means of pulsed potentiostatic reduction of graphene oxide (GO) on a glassy carbon electrode (GCE). The resulting electrode (ERGO/GCE) was characterized by cyclic voltammetry (CV) and scanning electron microscopy (SEM). The electrochemical behaviors of baicalein at the ERGO/GCE were investigated in detail by CV, chronoamperometry (CA) and chronocoulometry (CC). The experimental results demonstrated that the ERGO/GCE exhibited excellent response toward the redox of baicalein as evidenced by the significant enhancement of redox peak currents (i_p) and the decreased peak‐to‐peak separation (ΔE_p) in comparison with a bare GCE. Under the optimum experimental conditions, the reduction peak cureent was proportioanal to the baicalein concentration in the range of 5.0 × 10^‐9 ～ 5.0 × 10^‐7 mol L^‐1 with the detection limit of 2.0 × 10^‐9 mol L^‐1. The proposed method was also applied successfully to determine baicalein in spiked human blood serum samples.     

OH functionalized Multi-Walled Carbon Nanotube modified electrode as electrochemical sensor for the detection of Aceclofenac

ABSTRACT

The rapid electrochemical determination of Aceclofenac (ACF) has been employed by cyclic voltammetry (CV), differential pulse voltammetry (DPV) using developed OH-functionalised multiwalled carbon nanotube carbon paste electrode (OH-MWCNT/CPE). Modified electrode was characterised by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDAX), X-ray diffraction spectroscopy (XRD), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The ACF exhibits two oxidation peaks at +0.4 V, +0.66 V and one reduction peak at +0.3 V. The active surface area of the bare carbon paste electrode (BCPE) and modified electrode have been characterised by using K₃[Fe(CN)₆] solution containing 0.1 M KCl. In DPV mode, variation of ACF gave the limit of detection (LOD = 3s/m) 0.246 μM over the concentration range 1.0 to 190.0 μM (R² = 0.9994). The developed electrode has good stability, reproducibility and could be successfully validated for the detection of ACF in pharmaceutical samples and biological fluids.     

Electrodeposition CaCO3 Nanoparticles‐chitosan Composite Film on Carbon Ionic Liquid Electrode as a Platform for Hemoglobin Electrochemical Biosensor

By one‐step co‐electrodeposition CaCO₃ nanoparticles‐chitosan composite film on carbon ionic liquid electrode (CILE), and then by spreading the composition of hemoglobin (Hb) and chitosan on the nanoCaCO₃‐chi/CILE, a Hb‐chi/nanoCaCO₃‐chi/CILE was fabricated and the direct electrochemistry and electrocatalysis of Hb at the electrode was investigated. The electrochemical impedance spectroscopy of the modified electrode showed the electron transfer resistance was 1166 Ω. Investigation results of cyclic voltammetrys showed a pair of well‐defined and quasireversible redox peak of Hb with the formal potentials of ‐0.295 V (vs. SCE) in 0.1 mol·L^‐1 pH 7.0 PBS; the response time of the reduction peak currents of Hb was lower than 3s; a linear range for determination of H₂O₂ was from 5.0 μmol·L^‐1 to 1.3 mmol·L^‐1 with a detection limit of 1.6 μmol·L^‐1 (S/N = 3) and a sensitivity of 0.16 A·M^‐1·cm^‐2; the electron transfer rate constant and the apparent Michaelis‐Menten constant of Hb were 1.98 s^‐1 and 0.81 mmol·L^‐1, respectively. As a result, the case of the one‐step co‐electrodeposition and the promising feature of biocomposite could serve as a versatile platform for the fabrication of electrochemical biosensors.     

An Exfoliated Graphite Based Electrochemical Sensor for As(III) in Water

In this work, we present the application of an exfoliated graphite electrode modified with gold nanoparticles (AuNPs) for the detection of As(III) in acidic media. Gold nanoparticles were deposited on the surface of an exfoliated graphite electrode by electrodeposition at a potential window of ?0.2 V to 1.2 V. This was followed by activation in 0.5 M H₂SO₄ with 10 cycles from 0.6 V to 1.4 V. The modification of exfoliated graphite (EG) showed an increased electroactive surface area of the electrode and improved peak current output in a Fe(CN)₆^3?/4? redox probe. EG‐AuNPs electrode was used to detect As(III) in 1.0 M HNO₃ using square wave anodic stripping voltammetry (SWASV) technique at optimum conditions of pH 3, deposition potential of ?0.8 V, deposition time of 180 s, frequency of 5 Hz and pulse amplitude of 50 mV. The EG‐AuNPs electrode detected As(III) in solution to a limit of 0.58 ppb with regression of 0.9993. The method reported is simple, cheap and possesses good reproducibility. The developed electrochemical sensor was applied in the detection of As (III) in an industrial real water sample. The results of the real water sample analysis from the developed method are comparable with the inductively coupled plasma – optical emission spectroscopy (ICP‐OES) results.     

Electrochemistry and Electrocatalysis of a Nafion/Nano‐CaCO3/Hb Film Modified Carbon Ionic Liquid Electrode Using BMIMPF6 as Binder

In this paper a room temperature ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆) was used as binder for the construction of carbon ionic liquid electrode (CILE) and a new electrochemical biosensor was developed for determination of H₂O₂ by immobilization of hemoglobin (Hb) in the composite film of Nafion/nano‐CaCO₃ on the surface of CILE. The Hb modified electrode showed a pair of well‐defined, quasi‐reversible redox peaks with E_pa and E_pc as ?0.265 V and ?0.470 V (vs. SCE). The formal potential (E°′) was got by the midpoint of E_pa and E_pc as ?0.368 V, which was the characteristic of Hb Fe(III)/Fe(II) redox couples. The peak to peak separation was 205 mV in pH 7.0 Britton–Robinson (B–R) buffer solution at the scan rate of 100 mV/s. The direct electrochemistry of Hb in the film was carefully investigated and the electrochemical parameters of Hb on the modified electrode were calculated as α=0.487 and k_s=0.128 s^?1. The Nafion/nano‐CaCO₃/Hb film electrode showed good electrocatalysis to the reduction of H₂O₂ in the linear range from 8.0 to 240.0 μmol/L and the detection limit as 5.0 μmol/L (3σ). The apparent Michaelis–Menten constant (K_M^app) was estimated to be 65.7 μmol/L. UV‐vis absorption spectroscopy and FT‐IR spectroscopy showed that Hb in the Nafion/nano‐CaCO₃ composite film could retain its native structure.     

Electrochemical Study on the Interaction of Irinotecan with Calf Thymus Double Stranded DNA

Voltammetric behavior of Irinotecan (CPT‐11) was studied in a phosphate buffer (0.002 mol·L^?1, pH 7.5) solution at the hanging mercury drop electrode (HMDE) using cyclic voltammetry (CV). CPT‐11 showed two irreversible cathodic peaks at ?1.01 V and ?1.09 V which involved two electrons and two protons in each reduction step. In addition, the interaction of Irinotecan with double‐stranded calf thymus DNA (ds‐DNA) was studied by CV at the HMDE employing an irreversible electrochemical equation. As a result of the reaction with ds‐DNA, the reduction peaks related to CPT‐11 were shifted in a negative direction and the peak currents were decreased. The diffusion coefficients of CPT‐11 in the absence (D_f) and presence (D_b) of ds‐DNA were calculated as 2.8×10^?5 cm²·s^?1 and 1.6×10^?5 cm²·s^?1 respectively. The binding constant (K=1.0×10⁴ L·mol^?1), and binding site size (s=0.60) of CPT‐11 interacting with ds‐DNA were obtained simultaneously by non‐linear fit analysis. The results demonstrate that the main interaction mode of CPT‐11 with ds‐DNA is electrostatic.     

Surface modification and characterization of phenanthroline nanofilms on carbon substrate

Modification of glassy carbon (GC) surfaces with phenanthroline derivatives (PDs) such as 5‐amino‐1,10‐phenanthroline (5AP) and 5,6‐diamino‐1,10‐phenanthroline (56DAP) is described in this study. Surface modification experiments were performed by cyclic voltammetry (CV) scanning from + 1.2 to + 2.7 V at scan rate of 100 mV/s applying 30 potential scans in acetonitrile (CH₃CN) containing 1 mM PDs and 100 mM tetrabutylammoniumtetrafluoroborate (TBATFB). The presence of PDs on GC electrode was confirmed using CV, electrochemical impedance spectroscopy (EIS), contact angle measurements and ellipsometry and comparing with the results of bare GC electrode. A mechanism was proposed for the electrochemical modification of the GC electrode surface with PDs. The structure of the 5AP and 56DAP films was also discussed in the light of electrochemical and spectroscopic data. The complex‐forming ability of the modified surfaces against metal cations was investigated by square‐wave voltammetry (SWV). It was shown that surfaces having 1,10‐phenanthroline ligands with different functional groups were quite useful for the determination of transition metal ions. Copyright © 2010 John Wiley & Sons, Ltd.     

Voltammetric Determination of Hemoglobin Using a Pencil Lead Electrode

In this paper the electrochemical behavior of hemoglobin (Hb) immobilized on a pencil lead electrode (PLE) was investigated. Immobilization of Hb on the pencil lead electrode was performed by nonelectrochemical and electrochemical methods. In phosphate buffer solution with pH 7.0 Hb showed a pair of well‐defined and nearly reversible redox waves (the anodic and cathodic peak potentials are located at ?0.18 V and ?0.22 V, respectively). The dependence of the anodic peak potential (E_pa) on the pH of the buffer solution indicated that the conversion of Hb? Fe(III)/Hb? Fe(II) is a one‐electron‐transfer reaction process coupled with one‐proton‐transfer. In addition the effect of scan rate on peak currents and peak separation potential was investigated and electrochemical parameters such as α and k_s were calculated. In the second part of this work, the ability of the electrode for determination of Hb concentration was investigated. The results showed a linear dynamic range from 0.15 to 2 µM and a detection limit of 0.11 µM. The relative standard deviation is 4.1 % for 4 successive determinations of a 1 µM Hb solution.     

Electrochemical Behaviors of Resveratrol and Its Interaction with DNA

Electrochemical behavior of resveratrol was studied in Britton‐Robinson (B‐R) buffer solution (pH = 4.0) at glassy carbon electrode (GCE) using cyclic voltammetry (CV). Resveratrol showed an irreversible anodic peak at 0.570 V which was involving one electron and one proton. Also, the interaction of resveratrol with double‐stranded fish sperm DNA was investigated by linear sweep voltammetry (LSV) and UV‐vis spectra. The results showed that peak potentials shifted to more positive value and peak currents decreased in electrochemical experiment and the maximum absorption decreased with red shift in UV‐vis spectra experiment with the addition of DNA, indicating the resveratrol interacted with DNA by intercalating into the double helix of DNA. Besides, the binding of resveratrol with DNA, analyzed in terms of the cooperative Hill model, yields the association constant K_a = 3.18 × 10⁵ and a Hill coefficient m = 1.06.     

Voltammetric and Differential Pulse Stripping Study of Adenine on a Sol‐gel Derived Carbon Composite Electrode

This communication reports on the electrochemical investigation of adenine on a sol‐gel carbon composite electrode (CCE). Cyclic voltammetric (CV) technique is used to characterize the redox behavior of adenine at CCE. The peak current and peak potentials are dependent on the pH of the buffer solution. From the scan rate and peak current study, there is evidence of adsorption of adenine on the CCE. The parameters affecting the differential pulse stripping adsorption peak were systematically optimized. Under optimum conditions of E_acc=?0.10 and t_acc=60 s, a linear calibration plot was obtained, 2×10^?7–1×10^?6 M. This CCE is useful for the simultaneous analysis of adenine and guanine from denatured DNA.     

Electrodeposition of dendritic gold/silver nanaoparticles on disposable screen‐printed carbon electrode and its application of 4‐mercaptopyridine in in situ electrochemical surface‐enhanced Raman scattering

Column electrodes pretreated through oxidation–reduction cycles were traditionally used in electrochemical surface‐enhanced Raman scattering (SERS). In this study, a disposable screen‐printed carbon electrode was introduced into in situ electrochemical SERS through the electrodeposition of dendritic gold/silver nanoparticles (Au/AgNPs) onto the surface of the carbon working electrode to induce the SERS enhancement effect on the electrode. Scanning electron microscopy images showed that dendritic Au/AgNPs nanostructures could be fabricated under appropriate electrodeposition conditions and could present a minimum SERS factor of 4.25 × 10⁵. Furthermore, the absorbed behavior of 4‐mercaptopyridine was investigated under different potentials. The adsorption configuration was inferred to transform from ‘vertical’ to ‘lying‐flat’. The proposed new electrode combined with a portable Raman spectrometer could be useful in the identifying products or intermediates during electrochemical synthesis or electrochemical catalysis in in situ electrochemical SERS. Copyright © 2016 John Wiley & Sons, Ltd.     

Influence of the degree of surface oxidation of polycrystalline Rh electrodes on the underpotential deposition of Cu

The underpotential deposition of copper onto polycrystalline rhodium was studied as a function of the degree of oxidation of the electrode surface in acidic media using potentiodynamic techniques. Surface oxidation of the rhodium electrode was carried out using a triangular sweep potential between E _L (lower limit) and E _U (upper limit: 0.94≤E _U≤1.4 V). Cu electrodeposition was performed at the same time as the total or partial reduction of the oxidized species. The surface oxides produced at E _U≤1.09 V were completely reduced during Cu electrodeposition. In this case, the potentiodynamic I-E patterns for oxidative dissolution of Cu were characterized by three anodic peaks located at 0.41 V (peak I), 0.47 V (peak II) and 0.59 V (peak III) and the coverage degree by Cu, θ_Cu, was on the order of a monolayer. Surface oxides produced at E _U>1.09 V were partially reduced during the copper electrodeposition. In this case, the I-E profiles exhibited only two anodic peaks (II and III) and θ_Cu was <1. The Rh-oxygen species that remain on the electrode surface block the active sites of lower energy and modify the binding energy of strongly adsorbed Cu. Electronic Publication